JPH0751629B2 - Polyamide imide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyamide imide which is a novel polymer having excellent performances in all of heat resistance, mechanical properties, chemical / physical properties and molding properties. . More specifically, the present invention relates to a polyamide-imide having excellent heat resistance, sliding properties, impact resistance, moldability and the like.

[Conventional technology]

 Suitable for use with terephthalic acid, isophthalic acid, trimellitic acid, etc.
From aromatic polycarboxylic acid and aliphatic alkylenediamine
Melt-moldable polyamide or polyamide-imide
Have been proposed. For example, the present inventors
-98332 discloses terephthalic acid, trimellitic acid and
And polyamides produced from aliphatic alkylenediamines
Proposed imide, and Japanese Patent Publication No. Sho 49-36959,
In JP-A-59-53536, hexamethylenediamine and
Polyamide produced from terephthalic acid and isophthalic acid,
2,4,4-Trimethylhexamethylenediamine and terephthalate
Polyamide produced from acid and acid (Trogamide T )Such
Is proposed. These polyamides or polyamids
Although doimide has excellent melt moldability, it does not
For applications such as moving materials, heat resistance and impact resistance
Further, a thermoplastic resin having excellent sliding characteristics is required.

[Problems to be solved by the invention]

In view of such a situation of the transparent polyamide or polyamide-imide used for the molding material or the sliding material, the present inventors have considered that the heat resistance property, the impact resistance property and the sliding property, especially the heat resistance property. A new polyamide imide having excellent characteristics was studied earnestly. As a result, a terephthaloyl alkylenediamine component unit (a), an isophthaloyl alkylenediamine component unit (b) and a specific imide bond-containing component unit (c) and, if necessary, another imide bond-containing component unit (d). It has been found that the polyamide-imide consisting of is a novel polyamide-imide that achieves the above-mentioned object, and that the novel polyamide-imide is a molding material or sliding material having excellent heat resistance, impact resistance and sliding characteristics, Arrived

[Means for Solving Problems] and [Operation] According to the present invention, the general formula [I] A terephthaloyldiamine component unit (a) represented by the general formula [II] And an isophthaloyldiamine component unit (b) represented by the general formula [III] An imide bond component unit (c) represented by: [wherein, R ⁰ represents a divalent group having 4 to 25 carbon atoms. ]
(I) The composition of each component is in the range of 20 to 85 mol% of (a) component, 10 to 80 mol% of (b) component, and 5 to 60 mol% of (c) component. And the molar ratio of (a) component / (b) component is in the range of 85/15 to 20/80, and the molar ratio of [(a) component + (b) component] / (c) component is 97. In the range of / 3 to 5/95, and (ii) the divalent group R ⁰ is an R ¹ group which is an alkylene having 4 to 20 carbon atoms and a 6 to 25 carbon atom as described below. Specific diamine residue
It is composed of R ² , and the R ¹ group is in the range of 20 to 98 mol% and the R ² group is in the range of ^{2 to} 80 mol%, (iii) the MFR measured at 300 ° C. and a load of 10 kg is 0.1 or more, And the intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ℃ is 0.2-4dl / g
A polyamide-imide having the following range is provided as a substance patent.

The terephthaloyldiamine component unit (a) constituting the polyamideimide of the present invention has the general formula [I] [In the formula, R ⁰ represents a divalent group having 4 to 25 carbon atoms. ]
Is a terephthaloyldiamine component unit represented by
Its content is in the range of 20 to 85 mol%, preferably 30 to 80 mol%.

If the content of the component unit (a) is more than 85 mol%, the flexibility is lowered and the impact resistance is greatly lowered.

The isophthaloyldiamine component unit (b) constituting the polyamideimide of the present invention has the general formula [II] [In the formula, R ⁰ represents a divalent group having 4 to 25 carbon atoms. ]
Is an isophthaloyldiamine component unit, and its content is in the range of 10 to 80 mol%, preferably 20 to 70 mol%. When the content of the isophthaloyldiamine component unit is smaller than 10 mol% or larger than 80 mol%, the tensile strength, bending strength, Izod impact strength, heat aging resistance and the like are deteriorated.

The imide bond component unit (c) constituting the polyamide-imide of the present invention has the general formula [III] [In the formula, R ⁰ represents a divalent group having 4 to 25 carbon atoms. ]
The unit content of the component (c) is 5 to 60 mol%, preferably 10 to 40 mol%.
Is the range. When the content of the component (c) is less than 5 mol%, the impact resistance becomes low, and the content is 60 mol%.
If it exceeds, the heat resistance of the polyamide will deteriorate.

The imide bond-containing component unit (d) which may constitute the polyamideimide of the present invention has a general formula [IV] [IV] [In the formula, R ⁰ represents a divalent group having 4 to 25 carbon atoms. ]
And the content of the component (d) is 0 to 95 mol%, preferably 0 to 50 mol%.
It is particularly preferably in the range of 0 to 20 mol%. If the content of the component (d) is more than 95 mol%, the heat resistance of the polyamideimide will deteriorate.

The content of each component constituting the polyamideimide of the present invention is in the above range, the molar ratio of the component (a) / the component (b) is 85/15 to 20/80, preferably 80/20 to 40 /. The range is 60. In the polyamideimide, the molar ratio of [(a) component + (b) component] / (c) component is 95/5 to 30/70,
It is preferably in the range of 95/5 to 40/60. When the polyamide-imide contains the imide bond-containing component unit (d), [(a) component + (b) component] / [(c) component +
(D) component] has a molar ratio of 95/5 to 30/70, preferably 95/5
The range is up to 40/60. In the polyamide-imide,
If the molar ratio of component (a) / component (b) is greater than 85/15, impact resistance, heat aging resistance, etc. of the polyamide-imide will decrease, and [(a) component + (b) component] / (c ) Component or [(a) component + (b) component] / [(c) component +
If the molar ratio of (d) component] is larger than 97/3, the impact resistance and flexibility of the polyamideimide are deteriorated, and if it is smaller than 5/95, the heat resistance characteristics such as heat distortion temperature of the polyamideimide are deteriorated. become.

Further, the divalent group R ⁰ constituting the diamine component of the polyamideimide of the present invention is a group R ¹ which is an alkylene having 4 to 20 carbon atoms and a specific diamine residue having 6 to 25 carbon atoms as described later. Consists of the group R ^{2, the} group R ¹ being 5 to 98 mol%, preferably 20 to 98 mol%, particularly preferably 40 to 95 mol%.
In the range of ² to 95 mol% of R ² groups, preferably ² to 80
%, Particularly preferably 5 to 60 mol%.

The polyamideimide of the present invention may contain an insoluble component in concentrated sulfuric acid at 30 ° C. The MFR measured at 300 ° C. and a load of 10 kg of the polyamideimide needs to be 0.1 g / 10 minutes or more, and preferably 1 g / 10 minutes or more. When the polyamideimide is dissolved in concentrated sulfuric acid, [η] measured at 30 ° C. in concentrated sulfuric acid is 0.2 to 4 dl / g, preferably
The range is 0.3 to 3.5 dl / g, particularly preferably 0.5 to 3 dl / g.

The polyamideimide of the present invention may have crystallinity or may be amorphous. The crystallization rate increases as the content of the terephthaloylalkylenediamine component unit (a) represented by the general formula [I] constituting the polyamideimide increases. The crystallization rate of the polyamide-imide of the present invention is usually 7% or less, preferably 3% or less. When the polyamideimide of the present invention has crystallinity, its melting point is usually 250 to 360 ° C, preferably 280 to 350 ° C.
Is the range. The softening temperature of the polyamide-imide of the present invention is usually 150 to 370 ° C, preferably 160 to 350 ° C.

The above-mentioned general formulas [I] to [IV] of the polyamide-imide of the present invention
The alkylenediamine component corresponding to the alkylene group R ¹ in the constituent component represented by is an alkylenediamine component unit having 4 to 20 carbon atoms, and specifically, 1,4-diaminobutane, 1,5- Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,1
1-diaminoundecane, 1,12-diaminododecane, 1,1
3-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, Examples thereof include alkylenediamine components such as 1,20-diaminoeicosane. As these alkylenediamine components, only one kind may be contained alone or two or more kinds may be contained as a mixture. Among these alkylenediamine component units, those having 6 to 16 carbon atoms are preferable, and 1,6-diaminohexane component is particularly preferable.

The above-mentioned general formulas [I] to [IV] of the polyamide-imide of the present invention
The diamine component unit corresponding to R ² in the constituent component represented by is a diamine component unit having 6 to 25 carbon atoms selected from the following group.

Specific examples of the diamine component unit forming R ² include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl). Cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiverazine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4 ′
-Diamino-3,3 ', 5,5'-tetramethyldicyclohexylmethane, 4,4'-diamino-3,3', 5,5'-tetramethyldicyclohexylpropane, 4,4'-diamino-3,
3'-dimethyldicyclohexyl, 4,4'-diamino-3,
3 ', 5,5'-tetramethyldicyclohexyl, α, α'
-Bis (4-aminocyclohexyl) -p-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl) -m-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl) -1,4-cyclohexane , Α, α′-bis (4-aminocyclohexyl) -1,
3-cyclohexane etc. can be illustrated.

The polyamide-imide of the present invention is one in which the component (a), the component (b), the component (c) and, if necessary, the component (d) are randomly arranged and bonded to each other to form a chain structure.
Here, the chain structure is not limited to a straight chain structure, but may be a branched chain structure or a crosslinked structure between different molecules. The branched chain structure or the crosslinked structure is formed through the imide bond-containing component unit (d). The polyamideimide of the present invention includes a ternary polycondensate composed of a component (a), a component (b), and a component (c), a component (a),
There is a quaternary polycondensate composed of component (b), component (c) and component (d). Among the polyamideimides of the present invention, a polyamideimide having a linear or branched structure, that is, a substantially linear structure is preferable.

The molecular end of the polyamideimide of the present invention has an alkylenediamine component, a terephthalic acid component, an isophthalic acid component, a carboxyphthalic acid component, which constitutes the component (a), the component (b), the component (c) or the component (d), It may be any of the pyromellitic acid imide components.

When the molecular end is the alkylenediamine component, the terminal amine group may be acylated with a lower carboxylic acid, or a salt may be formed. When the molecular end is a terephthalic acid component, an isophthalic acid component unit or a carboxyphthalic acid component, the terminal carboxyl group may be esterified with a lower alcohol or may be amidated with an amine, It may form a salt or may form an acid anhydride.

The polyamide-imide of the present invention is obtained by polycondensing a corresponding diamine and an acid chloride such as terephthalic acid chloride, isophthalic acid chloride, trimellitic anhydride chloride and, if necessary, pyromellitic anhydride dichloride by a solution polymerization method or an interfacial polymerization method. , First, after synthesizing the corresponding polyamic acid, dehydration ring closure by heating,
The method of converting to the polyamideimide of the present invention may be adopted, and corresponding diamine and terephthalic acid, isophthalic acid, trimellitic acid (trimellitic anhydride may be used) and, if necessary, pyromellitic acid (pyromellitic acid anhydride may be used). It can also be synthesized by a solution or melt polycondensation method in the presence or absence of a carboxylic acid such as and water, a solvent such as phenol, gresol, and terphenyl, or an oligomer is produced by the above method. After that, a method in which a method for increasing the molecular weight by a solid phase polymerization method is used in combination can also be adopted. Further, a method in which a melt polycondensation reaction is allowed to proceed under heating using a kneader such as an extruder or a kneader to obtain a polymer can be employed.

The polyamideimide of the present invention may contain a polyamic acid before dehydration corresponding to the polyamideimide. The amount thereof is usually 30 mol% or less, preferably 10 mol% or less, based on the polyimide-forming functional group. Further, when synthesizing the polyamideimide of the present invention, a catalyst such as phosphoric acid, sodium hypophosphite, octyl phosphate, tristridecyl phosphite, a stabilizer and the like can be added.

The method for determining the constituent composition of the polyamideimide of the present invention, and the method for measuring the softening temperature, melting point, intrinsic viscosity [η] and crystallization rate are shown below.

(1) Composition of Polyamideimide Constituent Components Carbon, hydrogen and nitrogen atoms in polyamideimide are subjected to elemental analysis to determine their contents, and the sum of the carbon atom and hydrogen atom contents and the nitrogen atom content. The composition of the constituents of the polycondensate was determined from the ratio with.

(2) Softening temperature Using a melting point measuring device manufactured by Yanagimoto KK, polyamide crushed into fine powder in a mortar was used for the central part (about 1 cm ² ) of ^two preparations.
Sandwiched between the two, raising the temperature at a rate of 2 ° C./min, observing the temperature at which the polyamide begins to dissolve and the temperature at which all of the polyamide has dissolved,
The average value of these temperatures was defined as the softening temperature of the polyamide-imide.

(3) Melting point The differential thermal analysis of the resin was carried out at a temperature rising rate of 10 ° C. per minute using MJ-800-EY manufactured by Rigaku Denki KK.

(4) Intrinsic viscosity [η] The relative viscosity of 96 wt% concentrated sulfuric acid solution with resin temperature 0.500 g / dl, 0.77 g / dl, 1.00 g / dl at 30 ° C was measured with an Ubbelohde viscometer to obtain the specific viscosity. Was obtained, and [η] was obtained from these points by plotting. The above solution was prepared at 30 ° C.

(5) Crystallization rate A wide angle (2θ: 7
It was determined by performing X-ray analysis at 0 ° C to 3 ° C.

The polyamide-imide of the present invention is used for molding materials, sliding materials, fiber coating agents, adhesives, and various other applications. If necessary, conventionally known polymer stabilizers, plasticizers, release agents, lubricants, fillers and the like can be added to the polyamide. Examples of the polymer include polyamides such as nylon 6,6 and nylon 6, polyesters, polyethers, and α-olefin elastic bodies such as maleated ethylene propylene copolymers.

The polyamide-imide according to the present invention can form a composition for molding materials. This composition for molding material is composed of the above-mentioned polyamide imide [A] and filler [B]. The filler is an organic or inorganic compound having various forms such as powder, plate, fiber or cloth, and specifically, silica, alumina, silica-alumina, talc, diatomaceous earth, Clay, kaolin,
Quartz, glass, mica, graphite, molybdenum disulfide, gypsum, red iron oxide, titanium dioxide, zinc oxide, aluminum, copper, stainless steel, and other powdery or plate-like inorganic compounds, glass fiber, carbon fiber, boron fiber, ceramics Fibers, asbestos fibers, fibrous inorganic compounds such as stainless steel fibers or secondary processed products such as cloth-like products, polyparaphenylene terephthalamide,
Such as polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, a condensate of diaminodiphenyl ether and terephthalic acid (isophthalic acid), a condensate of p (m) -aminobenzoic acid, etc. Wholly aromatic polyamide, wholly aromatic polyamide imide such as diaminodiphenyl ether and condensation product of trimellitic anhydride or pyromellitic anhydride, wholly aromatic polyimide, polybenzimidazole,
Examples of the heterocyclic ring-containing compound such as polyimidazophenanthroline, and powdered, plate-shaped, fibrous or cloth-shaped secondary products such as polytetrafluoroethylene can be exemplified. The above may be mixed and used. As these fillers, those treated with a silane cutter or a titanium cutter can be used as well.

Among the above-mentioned fillers, it is preferable to use silica, silica-alumina, alumina, titanium dioxide, graphite, molybdenum disulfide, polytetrafluoroethylene as the powdery filler, and particularly graphite, molybdenum disulfide or polytetrafluoroethylene. The use of tetrafluoroethylene is preferable because the molded product obtained from the composition has improved wear resistance such as dynamic friction coefficient, Taber wear, and limit PV value. The average particle size of such fillers is usually 0.1 mμ or
The range of 200μ, particularly 1mμ to 100μ, is preferable because the above-mentioned wear resistance is remarkably improved. The proportion of the filler to be blended is usually in the range of more than 0 to 200 parts by weight, preferably more than 0 to 100 parts by weight, particularly preferably 100 parts by weight of the polyamide.
It is in the range of 1.0 to 50 parts by weight.

Further, among the above-mentioned fillers, examples of organic fibrous fillers include polyparaphenylene terephthalamide fibers, polymetaphenylene terephthalamide fibers, polyparaphenylene isophthalamide fibers, polymetaphenylene isophthalamide fibers, and diamino. When a wholly aromatic polyamide fiber such as a fiber obtained from a condensation product of diphenyl ether and terephthalic acid or isophthalic acid is used, the molded product obtained from the composition has mechanical properties such as tensile strength and Izod impact strength, and heat resistance. This is preferable because heat resistance characteristics such as deformation temperature are improved. Further, when glass fiber, carbon fiber or boron fiber is used as the inorganic fibrous filler among the above-mentioned fillers, the molded article obtained from the composition has a mechanical strength such as tensile strength, bending strength and bending elastic modulus. Properties, heat resistance such as heat distortion temperature, and chemical and physical properties such as water resistance are improved, which is preferable. When the average length of the organic or inorganic fibrous filler is usually in the range of 0.1 to 20 mm, particularly 1 to 10 mm, the moldability of the composition is improved and the molded product obtained from the composition is obtained. It is preferable because heat resistance characteristics such as heat deformation temperature and mechanical characteristics such as tensile strength and bending strength are improved. The mixing ratio of the organic or inorganic fibrous filler is usually 3 to 200 parts by weight, preferably 5 to 180 parts by weight, particularly preferably 100 parts by weight of the polyamide. Is in the range of 5 to 150 parts by weight.

The polyamide-imide produced by the method of the present invention can be molded by conventional melt molding such as compression molding, injection molding or extrusion molding.

〔Example〕

Next, the polyamide imide of the present invention and the composition thereof will be specifically described with reference to examples. The method for preparing the test piece and the method for evaluating each performance are shown below.

The following abbreviations used in the tables below indicate the following compounds, respectively.

TA: terephthalic acid IA: isophthalic acid TC: trimellitic anhydride C ₆ DA: 1,6-diaminohexane ACM: bis (4-aminocyclohexyl) methane AMC: 1,3-bis (aminomethyl) cyclohexane DMACM: bis (4 -Amino-3-methylcyclohexyl)
Methane (Preparation of test pieces and evaluation method for each physical property) Polyamideimide is crushed by a crusher (32 mesh pass) and dried for 12 hours at 100 ° C and 1 mmHg. After press-pressing at a temperature of 80 to 150 ° C. higher than Tg under a pressure of 100 kg / cm ^{2 in} the middle, and then cold pressing at a temperature of 20 ° C., a compression molded plate having a thickness of 2 mm to 10 mm was produced. These molded plates were cut into the dimensions of the test pieces shown in Table 1, dried in a nitrogen atmosphere at 100 ° C. under the conditions of 40 mmHg for 12 hours, and then subjected to the test.

In addition, the filler compounded product is a uniaxial extruder (L / D = 28, 20 m
mφ) and mixed to obtain strands of about 6 mm. The test piece was manufactured in the same manner as when the filler was not mixed.

[I] Polyamideimide Example 1 66.54 g (0.40 M) terephthalic acid, 155.26 g isophthalic acid
(0.94M), trimellitic acid 93.52g (0.45M), bis (4
-Aminocyclohexyl) methane 93.61g (0.45M) and hexamethylenediamine 155.14g (1.34M) together with 35g of ion-exchanged water were charged in one autoclave, and after sufficient N ₂ substitution, 250 ° C over 3 hours with stirring. The temperature was raised to. Furthermore, after allowing the reaction to proceed at 250 ° C for 1 hour in a sealed state, stirring was stopped and the pressure difference from the bottom of the autoclave was 35
The reaction mixture was discharged at kg / cm ² . 50 ℃ in N ₂ , 100mmHg
Then, it was dried for 24 hours to obtain a bottom condensate. This bottom secondary condensate [η] (in conc H ₂ SO ₄ , 30 ° C.) was 0.1 dl / g. 300 g of this bottom secondary condensate was transferred to a 0.5 polymerization flask, and atmospheric pressure, N
_The temperature was raised while stirring under ₂ atmospheres. The bottom condensate was completely melted at around 120 ° C. The temperature was raised to 250 ° C over about 5 hours, and then the reaction was carried out at 250 ° C for 1 hour. Further, the temperature was gradually raised to 300 ° C., and the reaction was allowed to proceed at 300 ° C. for 1 hour to obtain an amorphous polymer having a glass transition temperature of 160 ° C. The results are shown in Table 2.

Examples 2 to 6 and Comparative Examples 1 to 4 By the method described in Example 1, except that the charging ratio for acid decomposition, the type of diamine component, and the charging ratio in Example 1 were changed as shown in Table 2. Polyamideimide or polymer was synthesized. The results are shown in Table 2.

Comparative Example 5,6 2,4,4-Trimethylhexamethylenediamine and terephthalate
Polyamide consisting of acid and acid (Trogamide-T , Dyna
Mituto Nobel) and Mzerberke transparent
The performance of Liamide (Grillamide TR-55) is shown in Table 2.
It was

[II] Polyamideimide composition Example 7 Glass fiber reinforced consisting of 100 parts by weight of polyamideimide described in Example 1 and 50 parts by weight of glass fiber having an average length of 6 mm (Nippon Boshoku KK, Chip Strand CS 6PE-231). The polyamide-imide composition was produced under the extrusion conditions shown in Table 3. Table 3 shows the performance of the test pieces prepared by using this composition.
It was shown to.

Example 8 100 parts by weight of the polyamide-imide described in Example 1 and the amount of carbon fiber described in Table 3 (T008A manufactured by Toray KK,
A carbon fiber reinforced polyamide-imide composition having an average length of 6 mm) was produced under the extrusion conditions shown in Table 3. Table 3 shows the performance of the test pieces prepared using these compositions.

Example 9 100 parts by weight of the polyamide-imide described in Example 1
And the amount of polyparaphenylene terephthalate listed in Table 3.
Luamide fiber (Kevlar manufactured by Dyupon) 49, average length 3m
m) polyparaphenylene terephthalamide fiber
Reinforced polyamide composition prepared under extrusion conditions shown in Table 3
did. The performance of test pieces prepared using these compositions
The results are shown in Table 3.

Comparative Examples 7,8 Nylon-6,6 (Zytel 101 manufactured by Deupon) ) And po
Reacetal (Deuracon M- manufactured by Polyplastics Co., Ltd.
90 Table 3 shows the performance of the test piece prepared by using (1).

Comparative Example 9 210.2 (1 mol) of trimellitic acid, 116.21 g (1 mol) of hexamethylenediamine, 0.63 g of tristridecyl phosphite and 74 g of ion-exchanged water were charged in one autoclave, and N ₂ substitution was sufficiently performed. Then, the temperature was raised to 280 ° C. over 2 hours with stirring. Further, the reaction was allowed to proceed at 280 ° C. for 1 hour in a sealed state, the stirring was stopped, and the reaction mixture was taken out from the bottom of the autoclave at a differential pressure of 100 kg / cm ² . N ₂
A low-order condensate was obtained by drying overnight at 100 ° C. and 100 mmHg. The [η] of this low-order condensate (measured in the same manner as in Example 1) was 0.
It was 1 dl / g. This low-order condensate was subjected to polycondensation under melting with a twin-screw extruder to obtain a polymer having [η] of 1.10 dl / g. Physical properties were measured in the same manner as in Example 1. The results are shown in Table 4.
Shown in.

Comparative Example 10 A polymer was obtained in the same manner as in Comparative Example 9 except that the raw materials shown in Table 4 were used. Physical properties were measured in the same manner as in Example 1. The results are shown in Table 4.

Claims (1)

[Claims] 1. A general formula [I] A terephthaloylalkylenediamine component unit (a) represented by the general formula [II] And an isophthaloylalkylenediamine component unit (b) represented by the general formula [III] An imide bond component unit (c) represented by: [wherein, R ⁰ represents a divalent group having 4 to 25 carbon atoms. ]
(I) The composition of each component is in the range of 20 to 85 mol% of (a) component, 10 to 80 mol% of (b) component, and 5 to 60 mol% of (c) component. And the molar ratio of (a) component / (b) component is in the range of 85/15 to 20/80, and the molar ratio of [(a) component + (b) component] / (c) component is 97. / 3 to 5/95, and (ii) the divalent group R ⁰ is an R ¹ group which is an alkylene having 4 to 20 carbon atoms and 1,3-diaminocyclohexane, 1,4- Diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane,
1,4-bis (aminomethyl) cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiverazine,
Bis (4-aminocyclohexyl) methane, bis (4-
Aminocyclohexyl) propane, 4,4'-diamino-
3,3'-Dimethyldicyclohexylmethane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldicyclohexylmethane, 4,4'-diamino-3,3', 5,5'-tetramethyl Dicyclohexylpropane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, 4,4'-diamino-3,3 ', 5,
5'-Tetramethyldicyclohexyl, α, α'-bis (4-aminocyclohexyl) -p-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl)
-M-diisopropylbenzene, α, α'-bis (4-
Aminocyclohexyl) -1,4-cyclohexane, α,
Divalent residue having 6 to 25 carbon atoms derived from α'-bis (4-aminocyclohexyl) -1,3-cyclohexane
It is composed of R ² , and the R ¹ group is in the range of 20 to 98 mol% and the R ² group is in the range of ^{2 to} 80 mol%, (iii) the MFR measured at 300 ° C. and a load of 10 kg is 0.1 or more, And an intrinsic viscosity [η] measured in agricultural sulfuric acid at 30 ° C in the range of 0.2 to 4 dl / g.